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WO1995025775A1 - Compositions de refroidissement - Google Patents

Compositions de refroidissement Download PDF

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Publication number
WO1995025775A1
WO1995025775A1 PCT/GB1995/000556 GB9500556W WO9525775A1 WO 1995025775 A1 WO1995025775 A1 WO 1995025775A1 GB 9500556 W GB9500556 W GB 9500556W WO 9525775 A1 WO9525775 A1 WO 9525775A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
surface active
active agent
cooling
hydro
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB1995/000556
Other languages
English (en)
Inventor
Timothy James Noakes
Maurice Joseph Prendergast
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Publication of WO1995025775A1 publication Critical patent/WO1995025775A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/30—Materials not provided for elsewhere for aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/11—Ethers
    • C09K2205/112—Halogenated ethers

Definitions

  • the present invention relates to cooling compositions which are delivered from a spray device for the direct cooling of an article such as an electronic component.
  • the rapid cooling of articles such as electronic components using a low boiling point fluid delivered from a spray device is known in the art.
  • the low boiling point fluid is usually delivered by means of an aerosol and the aerosol product containing the fluid is often called a freezer spray or a freezer aerosol.
  • these freezer sprays are used to cool electronic components so as to locate faults, assess low temperature performance or to prevent damage during soldering.
  • various chlorofluorocarbons such as dichlorodifluoromethane (R-12) have found widespread use as the low boiling point fluid in these freezer sprays.
  • chlorofluorocarbons such as dichlorodifluoromethane have been implicated in the destruction of the earth's protective ozone layer, and there is general agreement that their manufacture and use should be severely restricted and eventually phased out completely. It is important, therefore, to replace the chlorofluorocarbons with materials having low or zero ozone depletion potentials.
  • R-12 refrigerant
  • R-134a 1,1,1,2-tetrafluoroethane
  • R-134a cannot be satisfactorily used as a direct substitute for R-12 in freezer spray applications since it tends to result in the generation of large quantities of electrostatic charge on the surface of the article being sprayed. This build-up of electrostatic charge will not only damage delicate electronic components but is also unsafe.
  • the present applicants have investigated this problem and have developed a cooling composition comprising a low boiling point fluid having a low or zero ozone depletion potential which does not lead to the generation of excessive amounts of electrostatic charge.
  • a cooling composition comprising at least one fluorine containing compound having a boiling point below 0°C selected from the (hydro)fluorocarbons and (hydro)fluorocarbon ethers and at least one surface active agent.
  • the present invention also provides a process for cooling an article which comprises contacting that article with a cooling composition comprising at least one fluorine containing compound having a boiling point below 0°C selected from the (hydro)fluorocarbons and (hydro)fluorocarbon ethers and at least one surface active agent.
  • the cooling composition of the invention will usually be delivered from a spray device by means of pressure acting on the composition and will normally be delivered as a liquid.
  • the present invention also provides a spray device for delivering a composition under the action of pressure comprising a spray head and a container holding the composition to be delivered from the spray head characterised in that the said composition is a cooling composition comprising at least one fluorine containing compound having a boiling point below 0°C selected from the (hydro)fluorocarbons and (hydro)fluorocarbon ethers and at least one surface active agent.
  • Suitable spray devices include aerosols in which the cooling composition is stored under pressure in a container with the at least one fluorine containing compound not only functioning as the cooling fluid but also as the propellant by creating the pressure necessary to drive the cooling composition from the container.
  • a (hydro)fluorocarbon is a compound selected from the group consisting of the hydrofluorocarbons and the perfluorocarbons
  • a (hydro)fluorocarbon ether is a compound selected from the group consisting of the hydrofluorocarbon ethers and the perfluorocarbon ethers.
  • the cooling composition may contain a mixture of two or more fluorine containing compounds, including a mixture containing a (hydro)fluorocarbon and a (hydro)fluorocarbon ether.
  • the (hydro)fluorocarbons and/or (hydro)fluorocarbon ethers which are used in the cooling compositions of the present invention will preferably have a boiling point below -10"C, more preferably below -15°C and particularly preferably below -20°C.
  • the preferred cooling compositions comprise one or more fluorine containing compounds selected from the hydrofluorocarbons and the hydrofluorocarbon ethers, and of these cooling compositions comprising one or more hydrofluorocarbons are particularly preferred.
  • Suitable hydrofluorocarbon ethers may be selected from the group consisting of trifluoromethyl difluoromethyl ether (CF.OCF H), pentafluoroethyl difluoromethyl ether (CF.CF_OCF_H) , 1,1,1,2-tetrafluoroethyl trifluoromethyl ether (CF CFHOCF ) and trifluoromethyl fluoromethyl ether (CF,OCFH_).
  • CF.OCF H trifluoromethyl difluoromethyl ether
  • CF.CF_OCF_H pentafluoroethyl difluoromethyl ether
  • CF CFHOCF 1,1,1,2-tetrafluoroethyl trifluoromethyl ether
  • CF,OCFH_ trifluoromethyl fluoromethyl ether
  • the preferred hydrofluorocarbons for use in the cooling compositions of the invention are selected from the C. , hydrofluorocarbons and particularly the C hydrofluoroalkanes.
  • C _ hydrofluoroalkanes which may be used in the cooling compositions of the present invention include, inter alia, trifluoromethane, fluoromethane, difluoromethane, pentafluoroethane, 1,1,1-trifluoroethane, 1, 1,2,2-tetrafluoroethane,
  • Cooling compositions comprising one or more hydrofluoroethanes form a particularly preferred embodiment of the present invention, and of these cooling compositions comprising 1,1,1,2-tetrafluoroethane (R-134a) are especially preferred.
  • the surface active agent which also forms an essential component of the cooling compositions of the present invention, may be of the anionic, cationic, nonionic or amphoteric variety and may be selected from any of the surface active agents known in the art. Liquid surface active agents are preferred to solid surface active agents since solid materials may leave undesirable deposits on the surface of the article being sprayed. Additionally, of the four classes of surface active agents listed above, nonionic and especially cationic surface active agents have been found to be particularly effective in that only very small concentrations of these materials are needed in the cooling composition to adequately suppress the accumulation of electrostatic charge on the surface of the article being sprayed.
  • the preferred cooling compositions comprise one or more nonionic and/or cationic surface active agents, and of these cooling compositions comprising one or more cationic surface active agents are particularly preferred. Mixtures of two or more surface active agents may be used if desired including mixtures comprising more than one class of surface active agent .
  • Suitable nonionic surface active agents include the polyethers. These materials, which are also known as alkoxylates, have a polyether chain which contains repeating units derived from an alkylene oxide, typically ethylene and/or propylene oxide.
  • the preferred cationic surface active agents for use in the cooling compositions of the invention are the quaternary ammonium salts since these materials have been found to be capable of providing the required suppression of electrostatic charge at extremely low concentrations in the cooling composition.
  • Quaternary ammonium salts as a class of surface active agents, are well known to those versed in the art. They typically contain a long chain aliphatic hydrocarbon group, such as a long chain alkyl group, and a selection of other organic moieties and possibly hydrogen bonded to the ammonium N atom. There will, of course, be a positive charge associated with the ammonium grouping, and so quaternary ammonium salts will also contain a salt forming counterion which will bring with it an associated negative charge.
  • the long chain aliphatic hydrocarbon group will tend to be linear but may contain a degree of branching and will typically contain from 10 to 20 carbon atoms.
  • a given material may, of course, contain both linear and branched hydrocarbon groups.
  • a typical quaternary ammonium salt surface active agent will contain one or more compounds having the formula:
  • R is a linear or branched long chain aliphatic hydrocarbon group, particularly a linear or branched long chain alkyl group and especially a linear or branched C ⁇ n _ smiling n alkyl group; each of X, Y and Z are independently H or an organic moiety, particularly a short chain alkyl group or an alkoxylate group; and
  • A is a counterion.
  • each of X, Y and Z are preferably independently selected from the short chain alkyl groups and the alkoxylate groups containing repeating units derived from one or more alkylene oxides.
  • Preferred short chain alkyl groups are the C, . alkyl groups, with methyl being an especially preferred short chain alkyl group.
  • Preferred alkoxylate groups are selected from the ethoxylates, the propoxylates and the ethoxylates-propoxylates which contain repeating units derived from one or both of ethylene oxide and propylene oxide.
  • the alkoxylate chain will typically contain from 1 to 100 and more typically from 1 to 50 repeating units derived from the alkylene oxide.
  • the preferred counterions for A are the halide ions, especially bromide and chloride, and the methosulphate (CH.SO.) and ethosulphate (CH CH ? SO.) ions.
  • the methosulphate and ethosulphate ions are particularly preferred on account of their low corrosivity.
  • the present cooling compositions may contain as much as 1.0 % by weight of the surface active agent, or even more, very small quantities of the surface active agent, e.g. of the order of 0.1 to 10,000 ppm (parts per million) by weight, have been found to be satisfactory in terms of providing a cooling composition which does not generate excessive amounts of electrostatic charge on the surface of the article on which it is being sprayed. This is clearly advantageous, since the problem of residual surface active agent remaining on the surface of the article can be much reduced or even eliminated.
  • the cooling composition will contain from 0.1 to 5,000 ppm, preferably from 0.1 to 2,000 ppm, more preferably from 0.1 to 1,000 ppm and particularly preferably from 0.1 to 500 ppm of the surface active agent on a weight basis.
  • Especially preferred cooling compositions contain less than 100 ppm by weight of the surface active agent.
  • the cooling composition may also contain a solubilising agent to aid the dissolution of the surface active agent in the one or more fluorine containing compounds constituting the cooling fluid.
  • Suitable solubilising agents may be selected from the alcohols, particularly the C, alkanols, with ethanol being especially preferred. If a solubilising agent is employed in the cooling composition, it will usually be present in an amount of from 0.001 to 10.0 % by weight, preferably in an amount of from 0.001 to 1.0 % by weight on the total weight of the composition.
  • the present invention is now illustrated but not limited by the following examples.
  • the cooling compositions tested were delivered using a spray device fitted with an aerosol valve.
  • the surface active agent was dissolved in ethanol (a solubilising agent) to give a 10 % v/v solution, i.e. a solution containing 10 % by volume of the surface active agent and 90 % by volume of the ethanol. A certain volume of this solution, which was different for each example so as to vary the amount of the surface active agent in the cooling composition, was then charged to the spray device followed by about 40 g of the R-134a.
  • the electrostatic test rig comprised a stainless steel target disc which was electrically insulated and connected to an electrostatic voltmeter for recording the electrostatic charge generated on the surface of the disc as a result of the spraying operation.
  • the spray device containing the cooling composition to be tested was held about 5 cm away from the stainless steel target disc and the cooling composition, which formed a liquid jet, aimed at the centre of the disc. Spraying was continued for 5 seconds. The charge generated on the surface of the disc as a result of the spraying was monitored by the electrostatic voltmeter and the maximum charge displayed on the digital read-out was recorded.
  • the surface active agent was dissolved in ethanol (a solubilising agent) to give a 1 % v/v solution, i.e. a solution containing 1 % by volume of the surface active agent and 99 % by volume of the ethanol.
  • ethanol a solubilising agent
  • a certain volume of this solution which was different for each example so as to vary the amount of the surface active agent in the cooling composition, was then charged to the spray device followed by about 40 g of the R-134a.
  • the electrostatic test rig comprised a stainless steel target disc which was electrically insulated and connected to an electrostatic voltmeter for recording the electrostatic charge generated on the surface of the disc as a result of the spraying operation.
  • the spray device containing the cooling composition to be tested was held about 5 cm away from the stainless steel target disc and the cooling composition, which formed a liquid jet, aimed at the centre of the disc. Spraying was continued for 5 seconds. The charge generated on the surface of the disc as a result of the spraying was monitored by the electrostatic voltmeter and the maximum charge displayed on the digital read-out was recorded.
  • the surface active agent was dissolved in 5 ml of ethanol (a solubilising agent) and 50 ⁇ l of this solution were then charged to the spray device followed by about 40 g of the R-134a.
  • the concentration of the surface active agent in the cooling composition was about 100 ppm on a weight basis.
  • the cooling composition was then subjected to an electrostatic spray test as before. The charge generated on the surface of the disc as a result of the spraying was monitored by the electrostatic voltmeter and peaked at -0.140 kV.
  • the cooling composition was then subjected to an electrostatic spray test as before.
  • the charge generated on the surface of the disc as a result of the spraying was monitored by the electrostatic voltmeter and peaked at -100 volts (V).
  • Example 14 The cooling composition was then subjected to an electrostatic spray test as before. The charge generated on the surface of the disc as a result of the spraying was monitored by the electrostatic voltmeter and peaked at -0.6 kV. Example 14
  • the cooling composition was then subjected to an electrostatic spray test as before.
  • the charge generated on the surface of the disc ' as a result of the spraying was monitored by the electrostatic voltmeter and peaked at -0.6 kV.
  • a certain volume of the surface active agent which was different for each example so as to vary the amount of the surface active agent in the cooling composition, was charged to the spray device followed by about 100 g of the R-134a.
  • SAA means surface active agent.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Composition de refroidissement comprenant au moins un composé contenant du fluor dont le point d'ébullition est inférieur à 0 °C, ce composé étant sélectionné entre les (hydro)fluorocarbones et les éthers d'(hydro)fluorocarbones et au moins un tensio-actif. On décrit également un procédé de refroidissement d'un article à l'aide de ladite composition de refroidissement et un dispositif de pulvérisation contenant cette dernière.
PCT/GB1995/000556 1994-03-22 1995-03-15 Compositions de refroidissement Ceased WO1995025775A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9405594.4 1994-03-22
GB9405594A GB9405594D0 (en) 1994-03-22 1994-03-22 Cooling compositions

Publications (1)

Publication Number Publication Date
WO1995025775A1 true WO1995025775A1 (fr) 1995-09-28

Family

ID=10752265

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1995/000556 Ceased WO1995025775A1 (fr) 1994-03-22 1995-03-15 Compositions de refroidissement

Country Status (2)

Country Link
GB (1) GB9405594D0 (fr)
WO (1) WO1995025775A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1096753A (en) * 1965-05-10 1967-12-29 Yardley & Company Ltd Collapsible foam pre-electric shave lotion
US4352789A (en) * 1980-03-17 1982-10-05 Minnesota Mining And Manufacturing Company Aerosol compositions containing finely divided solid materials
EP0176018A1 (fr) * 1984-09-24 1986-04-02 Henkel Kommanditgesellschaft auf Aktien Mousse décapante
EP0518601A1 (fr) * 1991-06-10 1992-12-16 Schering Corporation Formulations d'aérosols non-chlorofluorocarbonés
WO1994007971A1 (fr) * 1992-09-25 1994-04-14 E.I. Du Pont De Nemours And Company Compositions azeotropiques ou analogues a des azeotropes de gaz ammoniaque et d'hydrofluorocarbures

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1096753A (en) * 1965-05-10 1967-12-29 Yardley & Company Ltd Collapsible foam pre-electric shave lotion
US4352789A (en) * 1980-03-17 1982-10-05 Minnesota Mining And Manufacturing Company Aerosol compositions containing finely divided solid materials
EP0176018A1 (fr) * 1984-09-24 1986-04-02 Henkel Kommanditgesellschaft auf Aktien Mousse décapante
EP0518601A1 (fr) * 1991-06-10 1992-12-16 Schering Corporation Formulations d'aérosols non-chlorofluorocarbonés
WO1994007971A1 (fr) * 1992-09-25 1994-04-14 E.I. Du Pont De Nemours And Company Compositions azeotropiques ou analogues a des azeotropes de gaz ammoniaque et d'hydrofluorocarbures

Also Published As

Publication number Publication date
GB9405594D0 (en) 1994-05-11

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